JPH11194536A - Toner for developing electrostatic images - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for developing an electrostatic charge image which is excellent in low-temperature fixing property and high-temperature offset resistance and can obtain a high-quality image even if the particle size is reduced. SOLUTION: The binder resin contains two or more of a vinyl copolymer, a polyester resin and a resin in which the vinyl copolymer and the polyester resin are chemically reacted,
(A) Mw ≧ 100,000, Mw / Mn ≧ 20, (b)
5% by weight or more of a high molecular weight component having a molecular weight of 100,000 or more, and (c) the ratio (A _H : wt%) of the vinyl copolymer component constituting the high molecular weight component having a molecular weight of 100,000 or more and the polyester resin Composition ratio H of component ratio (B _H : wt%)
(= 100 × A _H / (A _H + B _H )) and a molecular weight of 10
Constituent ratio L (= 100 × A _L / (A) of the ratio of the vinyl copolymer component (A _L : wt%) and the proportion of the polyester resin component (B _L : wt%) constituting less than 10,000 low molecular weight components _L +
B _L )) satisfy the following relationship: 15 ≦ H ≦ 50, 5 ≦ L ≦ 40, and H> L.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, and an electrostatic printing method.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Numerous methods are known as described in Japanese Patent Publication No. JP-B-43-24748 and Japanese Patent Publication No. 43-24748. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, a toner image is formed on a transfer material such as paper. After the transfer, the toner image is fixed by heating, pressure, heating / pressing or solvent vapor to obtain a toner image.

As a method for fixing the toner image on a sheet such as paper, which is the last step, the most common fixing method at present is a pressure heating method using a heating roller.

In this method, fixing is performed by passing a toner image surface of a sheet to be fixed under pressure onto a surface of a heating roller having a surface formed of a material having a releasable property with respect to toner. is there.

According to this method, since the surface of the heating roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and Fixing can be performed.

However, in this method, since the surface of the heating roller and the toner image come into contact with each other under pressure in a molten state, a part of the toner image adheres and transfers to the surface of the fixing roller, and the toner image is re-transferred to the next sheet to be fixed. Transfer causes a so-called offset phenomenon, which causes a problem that the sheet to be fixed is soiled. Therefore, it is necessary to have excellent low-temperature fixing property and high-temperature offset resistance.

Heretofore, vinyl resins such as polyester resins and styrene resins have been mainly used as toner resins. Polyester resins originally have excellent low-temperature fixability, but also have the drawback of easily causing an offset phenomenon at high temperatures. Attempts to increase the viscosity by increasing the molecular weight of the polyester resin to compensate for this drawback not only impair the low-temperature fixability, but also degrade the pulverizability during toner production, making it unsuitable for finer toner particles. It will be something.

[0008] Vinyl copolymers such as styrene resins are excellent in pulverizability at the time of toner production and high in high molecular weight, and thus are excellent in high-temperature offset resistance. If the molecular weight is too low, the blocking resistance and the developability deteriorate.

[0009] In order to make the best use of the advantages of these two types of resins and to compensate for the drawbacks, several methods of mixing and using these resins have been studied. For example, JP-A-54-1
Japanese Patent No. 14245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer. However, the compatibility between the polyester resin and the vinyl copolymer is inherently poor, and unless the compounding ratio of these resins is appropriate, the low-temperature fixing property, high-temperature offset resistance, and blocking resistance are all satisfied. Hard to do. In addition, the dispersibility of the coloring agent, wax and the like added during the production of the toner becomes insufficient, so that a problem is likely to occur in the developability. In particular, in recent years, this problem is remarkable in a toner in which fine particles are advanced.

Further, JP-A-56-116043 and JP-A-58-159546 disclose a toner containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin. Is disclosed. JP 5
JP-A-8-102246 and JP-A-1-156759 disclose toners characterized by containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester. JP-A-2-881 discloses a toner containing a polymer obtained by esterifying an acid value-containing styrene resin and a polyester resin. In these methods, although the compatibility between the polyester resin and the vinyl copolymer is improved, a toner having a wide fixing temperature range and excellent offset resistance still needs to be improved together with the image characteristics described below. Have left.

That is, in recent years, it has been desired to improve the quality of a copied image by making the toner finer. But,
Even though the resolution and sharpness of an image can be increased by making the toner finer, various problems arise.

First, the fixability of the halftone portion deteriorates due to the reduction in the particle size of the toner. This is because the amount of applied toner in the halftone portion is small, the amount of heat transferred from the heating roller to the toner transferred to the concave portion of the fixing sheet is extremely small, and the fixing pressure is also suppressed by the convex portion of the fixing sheet. Because it will be worse. Further, since the toner transferred to the convex portion of the sheet to be fixed in the halftone portion has a small toner layer thickness, the shearing force applied to each toner particle is much larger than that of the solid black portion having a large toner layer thickness. Therefore, an offset phenomenon occurs, and a low-quality image is obtained.

Further, by reducing the particle size of the toner having a problem of fogging, the surface area of the toner is increased, so that the width of the charge amount distribution is increased and fogging is easily caused.

At present, there is no toner that solves the various problems described above.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to provide excellent low-temperature fixability, high-temperature offset resistance and blocking resistance, and to provide an excellent halftone portion even when the particle size is reduced. An object of the present invention is to provide a toner for developing an electrostatic image, which exhibits excellent fixability and has excellent developability over a long period of time.

[0016]

According to the present invention, there is provided a toner for developing an electrostatic image containing at least a binder resin and a colorant, wherein the binder resin comprises a vinyl copolymer, a polyester resin and a vinyl copolymer. In a gel permeation chromatography (GPC) of a tetrahydrofuran (THF) -soluble component of the toner, the resin contains two or more of resins chemically reacted with a polyester resin.
Mw ≧ 100,000, Mw / Mn ≧ 20, (b) 5% by weight or more of a high molecular weight component having a molecular weight of 100,000 or more, and (c) vinyl type constituting a high molecular weight component having a molecular weight of 100,000 or more Constituent ratio H (= ratio of copolymer component (A _H : wt%) and ratio of polyester resin component (B _H : wt%))
100 × A _H / (A _H + B _H )), the ratio of the vinyl copolymer component constituting the low molecular weight component having a molecular weight of less than 100,000 (A _L : wt%) and the ratio of the polyester resin component (B _L : Weight%) of the composition ratio L (= 100 × _AL / ( _AL +
B _L )) satisfies the following relationship: 15 ≦ H ≦ 50 Expression (1) 5 ≦ L ≦ 40 Expression (2) H> L Expression (3) About.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the toner of the present invention, the molecular weight and the molecular weight distribution of a vinyl copolymer and a polyester resin used as a binder resin are defined, and a high molecular weight component and a low molecular weight component are used as a vinyl copolymer. By optimizing the composition ratio of the polymer component and the polyester resin component as in the above formulas (1) to (3), it is possible to improve the low-temperature fixing property, the high-temperature offset resistance, and the pulverization property. In addition, the high molecular weight component having poor dispersibility of the release agent component due to the difference in viscosity contains a vinyl copolymer component having a value close to the solubility parameter of a commonly used release agent more than the low molecular weight component. By doing so, the dispersibility of the release agent in the toner is also improved, so that even if the toner is made into fine particles, a free wax component is not generated, and a toner having stable developability over a long period of time can be achieved. Become. Here, the "vinyl-based copolymer component" represents the sum of the vinyl-based copolymer and the vinyl-based copolymer chemically reacting with the polyester resin. Similarly, the “polyester resin component” represents the sum of the polyester resin and the polyester resin chemically reacting with the vinyl copolymer. In this method, THF-soluble components in a toner are separated into a high molecular weight component having a molecular weight of 100,000 or more and a low molecular weight component having a molecular weight of less than 100,000 by preparative liquid chromatography, and these are separated by ¹ H-NMR (nuclear magnetic resonance).
Each component can be quantified by the spectrum.

In the above formula, when H (proportion of the vinyl copolymer in the high molecular weight component) is less than 15%, the high-temperature offset resistance is deteriorated, and the effect of the polyester resin, which is originally poor in pulverizability, is reduced. Since the toner particles become remarkable, it is difficult to make the toner particles fine, and if it is attempted to make the particles fine, the production cost increases. When H is more than 50%, the high molecular weight vinyl copolymer impairs the low-temperature fixability. For this reason, H is 15 to 50%, preferably 2%.
0 to 40% is good.

Here, the composition ratio of the high molecular weight component has been described. In order to obtain the above-mentioned effects, the GPC molecular weight of the THF-soluble component of the toner must include at least 5% by weight of a component having a molecular weight of 100,000 or more. is necessary.

When L (the ratio of the vinyl copolymer in the low molecular weight component) is more than 40%, the low-temperature fixability deteriorates. When L is less than 5%, the compatibility with the high molecular weight component deteriorates, and when the toner is formed, poor dispersion of the colorant and the wax easily occurs. It cannot be realized. For this reason, L is 5 to 40%, preferably 5 to 30%.

When L is larger than H, it becomes difficult to balance low-temperature fixability and high-temperature offset resistance, so that HL> 0, preferably HL ≧ 5 is preferred.

In the present invention, the TH of the binder resin in the toner is
Although the composition ratio of the F-soluble component is described, the binder resin may contain a THF-insoluble component to such an extent that the above effects are not impaired. Specifically, TH in the total binder resin in the toner
The F-insoluble content is preferably 0 to 30% by weight.

The GP soluble in THF of the binder resin in the toner
In C, Mw needs to be 100,000 or more and Mw / Mn needs to be 20 or more. When Mw is smaller than 100,000, the high-temperature offset resistance deteriorates. When Mw / Mn is smaller than 20, it becomes difficult to balance low-temperature fixing property and high-temperature offset resistance.

In order to produce such a resin, it is preferable to synthesize it by the following production method. (1) Radical polymerization of a vinyl monomer in the presence of an unsaturated polyester resin. (2) A polyester resin is produced in the presence of a vinyl copolymer having a functional group. (3) A vinyl monomer is mixed with a polyhydric alcohol and a polycarboxylic acid, and a radical polymerization and an esterification reaction are carried out simultaneously or stepwise to produce.

In (1) and (2), a low molecular weight polymer and a high molecular weight polymer are separately produced, or the other polymer is produced in the presence of either polymer. The mixing ratio of the polymer can be controlled by successively changing the composition of the monomer (vinyl monomer, acid, alcohol).

Examples of the polyester resin monomer used in the present invention include the following.

Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (A);

[0028]

Embedded image

A diol represented by the formula (B):

[0030]

Embedded image And the like.

Examples of the divalent carboxylic acid containing 50 mol% or more of the total acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; succinic acid, adipic acid, sebacic acid, Alkyl dicarboxylic acids such as azelaic acid or anhydrides thereof, and succinic acids or anhydrides thereof further substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms; succinic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid; Saturated dicarboxylic acids or anhydrides thereof are exemplified.

Further, glycerin, pentaerythritol, sorbit, sorbitan,
Polyhydric alcohols such as oxyalkylene ether of a novolak type phenol resin are exemplified, and polycarboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydride thereof are exemplified as an acid component.

The alcohol component of the polyester resin particularly preferred in the practice of the present invention is a bisphenol derivative represented by the above formula (A), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, or succinic acid. And dicarboxylic acids such as n-dodecenylsuccinic acid or anhydride thereof, fumaric acid, maleic acid and maleic anhydride. Preferable examples of the crosslinking component include trimellitic anhydride, benzophenonetetracarboxylic acid, pentaerythritol, and oxyalkylene ether of a novolak type phenol resin.

The following are examples of the vinyl-based monomer for producing the vinyl-based resin.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p -Methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene,
styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride; Vinyl halides such as vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate ,
Isobutyl methacrylate, n-octyl methacrylate,
Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Α-methylene aliphatic monocarboxylic esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate Acrylates such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone ,
Vinyl ketones such as vinylhexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes;
Acrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide or methacrylic acid derivatives are exemplified.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic anhydride;
anhydrides of β-unsaturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene; Monomers having a hydroxyl group such as (hydroxy-1-methylhexyl) styrene are exemplified.

Further, if necessary, a polymer cross-linked with a cross-linkable monomer as exemplified below may be used.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene; examples of the diacrylate compound linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and above Compounds in which acrylate is replaced with methacrylate; examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol. 400 diacrylate, polyethylene glycol♯600 diacrylate, dipropylene glycol diacrylate, and methacrylate Include those obtained by changing the bets; as diacrylate compounds linked with a chain containing an aromatic group and an ether bond, such as polyoxyethylene (2)
-2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds were replaced with methacrylates. And polyester-type diacrylates, for example, trade name MANDA (Nippon Kayaku)
Is mentioned. Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and those obtained by replacing the acrylate of the above compound with methacrylate; Lucyanurate, triallyl trimellitate;

These cross-linking agents are used in combination with other monomer components 10
0.01 to 10 parts by weight (more preferably 0.03 to 5 parts by weight) can be used with respect to 0 parts by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of fixing property and offset resistance to a resin for toner include an aromatic divinyl compound (particularly divinylbenzene), a chain containing an aromatic group and an ether bond. Diacrylate compounds tied together.

In the present invention, the vinyl copolymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both components. Among the monomers constituting the polyester resin component, those which can react with the vinyl copolymer include, for example, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, and anhydrides thereof. Examples of the monomer constituting the vinyl copolymer component include those having a carboxyl group or a hydroxyl group, and acrylic acid or methacrylic acid esters.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co, Ni Or a metal such as Al, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

As the magnetic material, conventionally, triiron tetroxide (F
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe
₅ O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ -O ₁₂ ), copper iron oxide (CuF
e ₂ O _4), oxidation Tetsunamari (PbFe ₁₂ -O _19), iron oxide nickel (NiFe ₂ O _4), iron oxide, neodymium (NdFe
₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known, but according to the present invention, the above-mentioned magnetic materials are used alone or in combination of two or more. Particularly suitable magnetic materials for the purposes of the present invention are fine powders of triiron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
When the magnetic properties are about 79 μm and 795.8 kA / m is applied, the coercive force is 1.5 kA / m to 12 kA / m, and the saturation magnetization is 50 to 2 kA / m.
00 Am ² / kg (preferably 50-100 Am ² / k
g), those having a residual magnetization of ^{2 to 20} Am ² / kg are desirable.

The magnetic substance 1 was added to 100 parts by weight of the binder resin.
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

As the colorant irrespective of one component or two components, carbon black, titanium white, and any other pigments and / or dyes can be used. For example, when the toner of the present invention is used as a magnetic color toner, C.I. I. Direct Red 1,
C. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I.
I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic Green 6 and the like. Examples of pigments include: graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red-mouthed graphite, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G , Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indanthrene Blue BC,
Chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a two-component full-color toner, the following may be mentioned. Examples of the magenta coloring pigment include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1,52,53,54,55,57,58,60,6
3,64,68,81,83,87,88,89,9
0, 112, 114, 122, 123, 163, 20
2,206,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,1
3, 15, 23, 29, 35 and the like.

Although such a pigment may be used alone, it is more preferable to use the pigment and the pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image. Examples of such magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27, 30, 49, 81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,
22, 23, 24, 27, 29, 32, 34, 35, 3
6, 37, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25
And basic dyes such as 26, 27 and 28.

Other color pigments include cyan color pigments such as C.I. I. Pigment Blue 2, 3, 15,
16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by Chemical Formula 3.

[0051]

Embedded image

Examples of the coloring pigment for yellow include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the colorant is 0.1 to 60 parts by weight, preferably 0.5 to 60 parts by weight, based on 100 parts by weight of the binder resin.
50 parts by weight.

In the present invention, if necessary, one or more release agents may be contained in the toner particles.

The following are examples of the release agent used in the present invention. Aliphatic hydrocarbon-based waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, and paraffin wax; and aliphatic hydrocarbon-based waxes such as oxidized polyethylene wax, or block copolymers thereof; Examples of the wax include waxes mainly containing a fatty acid ester such as wax, sasol wax and montanic acid ester wax, and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax.
Furthermore, saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandinic acid, eleostearic acid, and vinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, and seryl alcohol And polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislaurin Saturated fatty acid bisamides such as acid amide and hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipamide, N, N'- Unsaturated fatty acid amides such as oleyl sebacic amide; aromatic bisamides such as m-xylene bisstearic acid amide and N, N'-distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, and stearic acid Fatty acid metal salts such as magnesium (commonly called metal soaps); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; behenic acid monoglyceride Partial esterified products of fatty acids and polyhydric alcohols; and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

As the wax particularly preferably used in the present invention, an aliphatic hydrocarbon wax is exemplified. For example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or a Ziegler catalyst under low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; A wax such as a synthetic hydrocarbon obtained from the distillation residue of the hydrocarbon obtained by the method or by hydrogenating them is preferred. Further, those obtained by performing separation of hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation, or a separation crystallization method are more preferably used. Hydrocarbons as bases are synthesized by a reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system) [for example, the Zintol method, the Hydrochol method (fluidized catalyst beds). Compound); hydrocarbons having a carbon number of up to about several hundreds obtained by the Aggé method (using a fixed catalyst bed) in which a large amount of waxy hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst The polymerized hydrocarbon is preferable since it is a straight-chain hydrocarbon having a small number of branches, a small number of branches, and a long saturation. Particularly, a wax synthesized by a method not based on the polymerization of alkylene is preferable in view of its molecular weight distribution.

In the molecular weight distribution of the wax, the molecular weight is 400
It is preferable that a peak exists in the region of ２2400, preferably 450 to 2000, particularly preferably 500 to 1600. By having such a molecular weight distribution, the toner can have favorable thermal characteristics.

The amount of the release agent used in the present invention is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the binder resin.

These release agents are usually added to the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution and adding and mixing while stirring, or by mixing at the time of kneading.

In the toner for developing an electrostatic image of the present invention, a charge control agent can be used if necessary in order to further stabilize the chargeability. The charge control agent is a resin component 100
0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight
It is preferred to use parts by weight.

Examples of the charge control agent include the following.

Organometallic complexes and chelate compounds are effective for controlling the toner to be negatively charged, for example, monoazo metal complexes; acetylacetone metal complexes;
Metal complexes or metal salts of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids are mentioned. Other examples include aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters and phenol derivatives such as bisphenol.

In order to control the toner to be positively charged,
Modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and oniums such as phosphonium salts which are analogs thereof Salts and their lake pigments; triphenylmethane dyes and these lake pigments (phosphor tungstic acid,
Phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanide compound, etc.); metal salts of higher fatty acids; Diorganotin borates such as dibutyl tin borate, dioctyl tin borate and dicyclohexyl tin borate; These can be used alone or in combination of two or more. Of these, charge control agents such as nigrosine compounds and quaternary ammonium salts are particularly preferably used.

As the fluidity improver used in the toner of the present invention, any material can be used as long as it can improve the fluidity by being added to the toner particles. For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder, wet-process silica, fine-powder silica such as dry-process silica, the silica is a silane coupling agent, a titanium coupling agent,
There is silica or the like treated by silicone oil or the like.

The preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halide, and is a so-called dry silica or fumed silica, which is produced by a conventionally known technique. Things. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production process, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide. Is also included. The particle diameter is desirably in the range of 0.001 to 2 μm as an average primary particle diameter, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm. .

Examples of commercially available fine silica powder produced by vapor phase oxidation of a silicon halide compound include those commercially available under the following trade names, for example.

AEROSIL (Aerosil Nippon) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, it is more preferable to use a treated silica fine powder obtained by subjecting a silica fine powder produced by the gas phase oxidation of the silicon halide compound to a hydrophobic treatment. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The hydrophobizing method is applied by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
For example, dimethylpolysiloxane having a hydroxyl group bonded to Si and having one siloxane unit as a terminal unit may be used. These are used alone or as a mixture of two or more.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight of a fluidizing agent with respect to 00 parts by weight.

To prepare the toner for developing an electrostatic image of the present invention, a binder resin, a colorant and / or a magnetic substance, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Then, using a hot kneader such as a kneader or an extruder, melting, kneading and kneading are performed to make the resins compatible with each other. After cooling and solidifying the melt-kneaded material, the solidified material is pulverized, and the pulverized material is classified. The toner of the present invention can be obtained.

Further, the fluidity improver and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having the fluidity improver on the surface of the toner particles.

The toner of the present invention has a volume average particle size of 2.5
The thickness is preferably from 6.0 to 6.0 μm from the viewpoint of high image quality and high image density.

The measurement methods of the molecular weight of the THF-soluble component, the ratio of the THF-insoluble component and the ¹ H-NMR of the toner according to the present invention are based on the following methods.

(1) Measurement of Molecular Weight The molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) is passed through the column at this temperature at a flow rate of 1 ml per minute. After dissolving the developer in THF and allowing it to stand overnight,
Filter with a 0.2 μm filter and use the filtrate as a sample. The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical
Co. Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 ×
10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10
⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 1
0 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶
It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

In order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns may be used in combination.
rs Co., Ltd. μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA-801, 802, 803, 804, 805, 8
06,807 are preferred.

(2) Measurement of THF Insoluble Content The toner is weighed, placed in a cylindrical filter paper (for example, No. 86R size 28 × 100 mm, manufactured by Toyo Roshi Kaisha, Ltd.) and subjected to a Soxhlet extractor. Extraction is performed for about 6 hours using 200 ml of THF as a solvent. At this time, extraction is performed at a reflux rate such that the THF extraction cycle is about once every 4 to 5 minutes. After completion of the extraction, the cylindrical filter paper is taken out and weighed to obtain an insoluble content of the polyester resin.

When the toner contains a THF-insoluble component such as a magnetic substance or a pigment other than the resin component, the weight of the toner put in the cylindrical filter paper is W ₁ g, and the weight of the extracted THF-soluble resin component is Assuming that W ₂ g and the weight of the THF-insoluble component other than the resin component contained in the toner is W ₃ , the content of the THF-insoluble component of the resin component in the toner is obtained from the following equation.

[0083]

(Equation 1)

FIG. 1 shows an example of a Soxhlet extraction apparatus. The THF 2 contained in the container 1 is heated and vaporized by the heater 8, and the vaporized THF is led to the cooler 5 through the pipe 7. The cooler 5 is constantly cooled by the cooling water 6. The THF cooled and liquefied by the cooler 5 is the cylindrical filter paper 3
When the liquid level of the THF accumulates in the storage part having the height of the middle pipe 4 and the THF is higher, the THF is discharged from the storage part to the container 1.
The toner contained in the cylindrical filter paper is extracted by the circulating THF.

(3) ¹ H-N in THF-soluble component in toner
Measurement of MR (nuclear magnetic resonance) spectrum Measurement device: FT NMR device JNM-EX400
(Manufactured by JEOL Ltd.) Measurement frequency: 400 MHz Pulse condition: 5.0 μs Data point: 32768 Delay time: 25 sec Frequency range: 10500 Hz Number of accumulations: 16 Measurement temperature: 40 ° C. Sample: 200 mg of a measurement sample is placed in a φ5 mm sample tube. And CDCl ₃ (THS 0.0
5%) and dissolved in a 40 ° C. thermostat to prepare.

(4) Measurement of Particle Size Distribution of Toner The measurement of the particle size distribution of the toner of the present invention uses a Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter Inc.). As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and a measurement sample is added to 2 to 20 ml.
Add mg. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and 2 μm using a 100 μm aperture as an aperture.
The volume distribution and the number distribution were calculated by measuring the volume and the number of the toners of m or more.

Then, a weight-based weight average particle diameter (D4) and a volume average particle diameter (Dv) obtained from the volume distribution according to the present invention (each median value of each channel is a representative value for each channel) are obtained. Was.

Hereinafter, the present invention will be described with reference to resin production examples and examples, but the present invention is not limited to these examples.

[0089]

Examples (Resin Production Example 1)-Terephthalic acid 25.9 mol%-Fumaric acid 12.7 mol%-Trimellitic anhydride 0.6 mol%-Bisphenol derivative represented by formula (A) (R: x + y in propylene group) = 2.2) 40.8 mol% (R: x + y = 2.2 in ethylene group) 20.0 mol% The above raw materials were charged together with an esterification catalyst into a 5-liter autoclave, and a reflux condenser, a water separator, and N ₂ gas were introduced. A tube, a thermometer and a stirrer were attached, and a polycondensation reaction was carried out at 230 ° C. while introducing N ₂ gas into the flask to obtain a polyester resin.

After completely dissolving 90 parts by weight of the polyester resin obtained in 100 parts by weight of xylene, 7.5 parts by weight of styrene and 2.5 parts by weight of 2-ethylhexyl acrylate were used.
Parts by weight and 0.1 parts by weight of azobisisobutyronitrile dissolved as a polymerization initiator were dissolved in a nitrogen atmosphere at about 1 part by weight.
At a temperature of 35 ° C., it was added dropwise over about 1 hour. By aging at the same temperature and removing the solvent, a resin A containing a polyester resin, a vinyl copolymer and a resin in which these were chemically reacted was obtained.

Next, 5.9 mol% of terephthalic acid, 32.7 mol% of fumaric acid, 7.0 mol% of trimellitic anhydride, bisphenol derivative represented by the formula (A) (R: x + y = 2.2 in propylene group) 35.0 mol% (R: x + y = 2.2 with ethylene group) 19.4 mol% was similarly subjected to a condensation polymerization reaction, and 75 parts by weight of the obtained polyester resin was dissolved in 100 parts by weight of xylene, and then 19 parts by weight of styrene. , 6 parts by weight of 2-ethylhexyl acrylate and 0.04 part by weight of the above polymerization initiator were added dropwise at a temperature of about 125 ° C. for about 3 hours in a nitrogen atmosphere. By aging at the same temperature and removing the solvent, a resin B containing a polyester resin, a vinyl copolymer and a resin in which these were chemically reacted was obtained.

In the resins A and B of the present invention, a vinyl resin
The copolymer reacts chemically with the polyester resin composition.
That is ,¹³Can be verified by C-NMR
You.

Generally, acrylic acid copolymerized with styrene
Ester group of ester of¹³Measured by C-NMR
The signal is that of the acrylate homopolymer.
Several pp toward high magnetic field due to the effect of benzene ring of styrene
The phenomenon of m shift is known. This phenomenon is an ester
The same applies when a polyester resin composition is present as the base
It is. Here, the carboxyl group of trimellitic acid
We focused on carbon.

The low-crosslinking polyester resin composition of ¹³ C-
The NMR measurement results in FIG. 2, a low degree of crosslinking polyester resin composition and the reaction was of styrene with 2-ethylhexyl acrylate having the same composition measurement result in FIG. 3, ¹³ C-NMR measurement of the binder resin A of the present invention FIG. 4 shows the results.

Table 1 shows the measurement results of each resin composition.

The resins A and B obtained as described above were
By melt-blending 0 parts by weight and 30 parts by weight, a binder resin (A) containing 25% by weight of a THF-insoluble content was obtained. The proportion of the vinyl copolymer in the THF-soluble matter of this resin was 12% by weight, and the proportion of the vinyl copolymer in the THF-insoluble matter was 32% by weight.

In the same manner, binder resins (a) to (e) were obtained by changing the composition ratio of the monomers.

(Resin Production Example 2) Terephthalic acid 25.0 mol% Maleic acid 13.0 mol% Dodecenyl succinic acid 7.0 mol% Bisphenol derivative represented by formula (A) (R: propylene group and x + y = 2. 2) 40.0 mol% (R: x + y = 2.2 in ethylene group) 15.0 mol% The above raw materials were charged together with an esterification catalyst into a 5-liter autoclave, and a reflux condenser, a water separator, a N ₂ gas inlet tube, and a temperature were used. A polycondensation reaction was performed at 230 ° C. while introducing a N ₂ gas into the flask with a meter and a stirrer to obtain a polyester resin.

Next, 14 parts by weight of styrene 6 parts by weight of butyl acrylate 0.02 parts by weight of azobisisobutyronitrile The above-mentioned material was dropped into 100 parts by weight of xylene heated to the reflux temperature over about 3 hours. did. Further, the polymerization was completed at about 140 ° C. under xylene reflux. Thereafter, 80 parts by weight of the above polyester resin is dissolved, and xylene is removed while heating to 200 ° C. under reduced pressure to obtain a binder resin (f) which is a mixture of the polyester resin and the vinyl copolymer. Was.

In the same manner as above, binder resins (G) to (G) were obtained by changing the composition ratio of the monomers.

Example 1 Binder resin (A) 100 parts by weight Azo-based iron complex compound 2 parts by weight Magnetic iron oxide 90 parts by weight (Average particle diameter 0.2 μm; Hc120 Oersted; σs65 emu / g; σr7emn / g) 4 parts by weight of low molecular weight polypropylene The above mixture was melt-kneaded with a biaxial extruder heated to 130 ° C, and the cooled mixture was coarsely pulverized with a hammer mill, and the coarsely pulverized product was finely pulverized with a jet mill. The finely pulverized product was classified by an air classifier to obtain a magnetic toner having a volume average diameter of 6.8 μm. The molecular weight of the toner soluble in THF was measured by GPC, and the low molecular weight component having a molecular weight of less than 200,000 and 20
As a result of being divided into 10,000 or more high molecular weight components, the content of the high molecular weight component was 15% by weight, the ratio L of the vinyl copolymer in the low molecular weight component was 12, and the ratio of the vinyl copolymer in the high molecular weight component was 12. The ratio was 30. Further, 2% of a THF insoluble content of the polyester resin in the toner was contained.

To 100 parts by weight of the magnetic toner, 1.0 part by weight of hydrophobic dry silica (BET 200 m ² / g) was externally added using a Henschel mixer to prepare a developer.

Using this developer, image characteristics were evaluated with a Canon digital copier GP-55, and good results were obtained as shown in Table 2. Further, when the fixing device of GP-55 was detached, an external drive and a temperature control function were provided, and the fixing speed was changed, and a fixing test was carried out, good results as shown in Table 2 were obtained.

Examples 2 to 5 The same procedure as in Example 1 was carried out except that the binder resin was changed to (A) to (E), and the molecular weight of the THF-soluble component and the proportion of the insoluble component in the toner were changed. Was as shown in Table 1.
When a test similar to that of Example 1 was performed, good results were obtained as shown in Table 2.

Comparative Examples 1 to 3 The same procedure as in Example 1 was carried out except that the binder resin was changed to (f) to (h). The molecular weight of the THF-soluble component and the ratio of the insoluble component in the toner are shown in Table 1. It began to show. When a test similar to that of Example 1 was performed, the results shown in Table 2 were obtained.

[0106]

[Table 1]

[0107]

[Table 2]

<Evaluation of Image> The image density is Macbeth.
It was measured by RD918 (manufactured by Macbeth).

Evaluation of fog was performed as follows. The fog density (%) was calculated from the difference between the whiteness of the white character portion of the printout image and the whiteness of the transfer paper measured by a "Reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.), and the fog was evaluated according to the following criteria.

Evaluation criteria: less than 1.2% △: 1.2 to less than 1.8% ・ ・ ・: 1.8 to less than 2.5% ×: 2.5 to Less than 4.0% × ... 4.0% or more

The density gradation was evaluated on a five-point scale: good ← ○, ○ △, Δ, Δ ×, × → bad.

[0112]

According to the present invention, by improving the binder resin of the toner, even if the toner is made into fine particles, no free coloring agent or wax is generated, the durability is excellent, and the low-temperature fixability and the low-temperature fixability are improved. The hot offset property is also sufficient.

[Brief description of the drawings]

FIG. 1 is a schematic illustration of a Soxhlet extractor.

FIG. 2 ¹³ C-NM of low cross-linking degree polyester resin composition
It is a figure showing an R measurement result.

FIG. 3 is a view showing the measurement results of styrene and 2-ethylhexyl acrylate having the same composition as that reacted with the low-crosslinking degree polyester resin composition.

FIG. 4 is a view showing a result of ¹³ C-NMR measurement of a binder resin A of the present invention.

Continuation of the front page (72) Inventor Kenichi Endo 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yuji 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. Inside

Claims (7)

[Claims] 1. A toner for developing an electrostatic image containing at least a binder resin and a colorant, wherein the binder resin is a vinyl copolymer, a polyester resin, and a chemical reaction between the vinyl copolymer and the polyester resin. In the gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble component of the toner, (a) Mw ≧ 100,000, Mw / Mn ≧ 20,
(B) 5% by weight or more of a high molecular weight component having a molecular weight of 100,000 or more, and (c) Ratio of a vinyl copolymer component constituting the high molecular weight component having a molecular weight of 100,000 or more (A _H : weight%) And H (= 100 × A _H / (A _H + B _H )), the ratio of the polyester resin component to the polyester resin component (B _H : wt%), and the vinyl copolymer component constituting the low molecular weight component having a molecular weight of less than 100,000 ratio of: the ratio of (a _L wt%) and the polyester resin component: composition ratio (B _L wt%) L (= 100 × a L /
(A _L + B _L )), wherein the following relationship is satisfied: 15 ≦ H ≦ 505 5 ≦ L ≦ 40 H> L. 2. The electrostatic image developing device according to claim 1, wherein the composition ratio H and the composition ratio L satisfy the following relationship: 20 ≦ H ≦ 405 ≦ L ≦ 30 H> L + 5. toner. 3. The vinyl copolymer component and / or the polyester resin component in the binder resin contains a monomer component capable of reacting with both components.
3. The toner for developing an electrostatic image according to item 1. 4. The toner for developing an electrostatic charge image according to claim 1, wherein the proportion of THF-insoluble components in the total binder resin in the toner is 0 to 30% by weight. . 5. The electrostatic image development according to claim 1, wherein the polyester resin in the toner is cross-linked by a trivalent or higher polyvalent carboxylic acid or a polyhydric alcohol. For toner. 6. The toner for developing an electrostatic image according to claim 1, wherein the colorant is a magnetic powder. 7. The electrostatic image developing toner according to claim 1, wherein the toner has a volume average particle diameter of 2.5 to 6.0 μm.